MATERIAU DE BASE SERVANT A LA PREPARATION DE PECTINES ET DE COMPOSES ASSOCIES, ET SON PROCEDE DE PREPARATION

A RAW MATERIAL FOR USE IN THE PREPARATION OF PECTIN AND RELATED COMPOUNDS, AND A METHOD FOR THE PREPARATION OF SAME

Abrégé français

L'invention porte sur un matériau de base servant à la préparation de pectines et de composés associés, ledit matériau consistant en pâte de betteraves à sucre pressée et stabilisée, puis soumise à un prétraitement biotechnique. Le prétraitement de l'invention consiste à abaisser le pH de pâte de betteraves à sucre fraîche pressée jusqu'à une valeur comprise entre 3,5 et 4,5 (de préférence entre 3,9 et 4,3) puis à stocker la pâte acidifiée dans une enceinte étanche, c.-à-d. sensiblement exempte d'air.

Abrégé anglais

The invention relates to a raw material for use in the preparation of pectin
and related compounds, the raw material being pressed, stabilized sugar beet
pulp subjected to biotechnical pre-treatment. In accordance with the invention
the raw material is prepared by pre-treating fresh pressed sugar beet pulp by
lowering the pH to a value between 3.5 and 4.5 (preferably 3.9 and 4.3) and
subsequently storing the obtained acid pulp in tight, i.e. substantially
oxygen-free conditions.

Revendications

6
CLAIMS
1. A raw material for use in the preparation of pectin and related
compounds, characterized by being purified, stabilized sugar beet
pulp subjected to biotechnical pre-treatment.
2. A raw material as claimed in claim 1, which has a pH of 3.5 to 4.5
(preferably 3.9 to 4.3) and 20 to 27 percent by weight of dry substance, and
is
substantially free from fermentable sugars and has been stored in
substantially
oxygen-free storage.
3. A method for the preparation of a raw material for use in the
preparation of pectin and related compounds, characterized by
pretreating fresh pressed sugar beet pulp by lowering the pH to a value
between
3.5 and 4.5 (preferably 3.9 and 4.3) and storing the acid pulp in
substantially
oxygen-free conditions.
4. A method of utilizing biotechnically pre-treated sugar beet pulp in
the preparation of pectin and related compounds, characterized by
fresh sugar beet pulp, from which sugar has been extracted, being pre-treated
by lowering the pH of the pulp to 3.5 to 4.5 (preferably about 4) and by the
acidified pulp being stored air-tightly for removal of oxygen and free sugars
in
an induced biotechnical reaction, whereupon the pulp is stored in tight
substantially oxygen-free conditions.
5. A method as claimed in claim 4, characterized by the use
of pressed pulp with no addition of lime or aluminium.
6. A method as claimed in claim 5, characterized in that the
pH is lowered by mixing a suitable acid or acid mixture with the pressed pulp.
7. A method as claimed in claim 6, characterized in that the
acid or acid mixture is mixed into pulp at a temperature of about 60°C,
preferably 50 to 60°C, i.e. preferably immediately after the pressing.

Description

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A RAW MATERIAL FOR USE IN THE PREPARATION OF PECTIN AND RELATED
COMPOUNDS, AND A METHOD FOR THE PREPARATION OF SAME
The invention is related to an improved method for the preparation
of organic materials, such as pectin, from sugar beet pulp, from which sugar
has been extracted. In accordance with the invention, said sugar beet pulp,
from which sugar has been extracted, is pre-treated in a biotechnical process
in mildly acidic, deoxidizing conditions prior to hydrolysis or extraction of
the
desired products. In the biotechnicai process the fresh pulp is subjected a de-
oxidizing, mildly acidic pre-treatment, and the pulp is allowed to stabilize
in
substantially oxygen-free conditions. The stabilized pulp, which is stable for
months in air-tight storage, is used as a raw material in the preparation of
sugar beet pectin and related products, such as araban, arabinose, galactan
and ferulic acids.
DESCRIPTION OF THE PRIOR ART
Sugar beet hemicellulose is a complex hydrocolloid based on galac-
turonic acid polymers, the backbone polymer chain comprising regions com-
posed of rhamnose and galacturonic acid for connecting polygalacturonic acid
units. Araban and galactan polymer chains are connected to the rhamnose
units in these hairy regions.
A galacturonic acid chain is partly acetylated and methylated. Xy-
lose and ferulic acid units are present in the side chains. Pectin can be ex-
tracted from sugar beet pulp after mild acid hydrolysis. The composition of
pectin depends on the extraction conditions. Some pectic substances, such as
arabans, can be alternatively extracted after alkaline hydrolysis. In his
patent
(US 5,008,254), Michael Weibel describes processes for carrying out the hy-
drolysis in acid conditions {pH below 4.5) or in alkaline conditions (pH over
9.0) at elevated temperatures.
WO 97/30215 (Wong, E., et al.) discloses use of fermented sugar
beet pulp for making paper or cardboard. The preparation of pectin and related
compounds is not disclosed.
A conventional process for the preparation of sugar beet pectin is
by acid hydrolysis at a pH of about 1.5, followed by neutralization,
purification
by filtration and precipitation of the pectins with alcohol. McCleary et al.
dis-
close an improved method of preparing araban from fresh sugar beet pulp by
extraction with an alkaline lime solution (US 5,250,306). Schiweck et al. pre-

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pared L-arabinose from sugar beet araban or beet pulp by hydrolysis in alka-
line conditions (US 4,81 fi,078).
The raw material for pedins has been either fresh or dried pulp.
Fresh pulp is available only for a short period during the sugar beet season.
Consequently, dried pulp has usually been employed.
ADVANTAGES OF THE INVENTION
The use of fresh pulp in the preparation of pedins is not economi-
cally feasible due to its limited availability. On the other hand, when the
pulp is
dried, reactions occur causing colour formation, lower quality of the products
obtained from the pulp, and reduced pectin yield. In practice no suitable raw
material for sugar beet pectin has been found, and consequently the produc-
tion and use of this excellent plant hydrocolloid has remained very low.
It has now been discovered that the use of non-dried sugar beet
pulp, from which sugar has been removed and which has been subjected to
biotechnical pre-treatment in acidic, deoxidizing conditions, results in an im
provement in the total process increasing the yields of the desired products
from the raw material, which remains stable in storage and is available
throughout the year. In the pre-treatment the free sugars still present in
said
pulp, from which sugar has been removed, are oxidized into organic acids and
oxygen is removed, but the pectic substances are not affected. Kept away
from light in tight storage, i.e. in substantially oxygen-free conditions, the
treated pulp remains stable for months. This stable pulp is an excellent raw
material in the preparation of sugar beet pectin and related compounds, such
as araban, galadan, L-arabinose, ferulic acids, L-rhamnose, etc.
DESCRIPTION OF THE INVENTION
Fresh, pressed sugar beet pulp, from which sugar has been ex-
traded and whose dry substance content is about 20 to 25 percent by weight,
is pre-treated by reducing its pH to about 4, preferably by mixing the pulp
with
a suitable acid solution. Organic acids, such as formic acid, lactic acid,
acetic
acid and/or mixtures thereof are effective and easy to use. Commercially
available acid mixtures include e.g. "Ensimax", which consists of formic acid
and lignosulphonate, and silage {AIV) acid consisting mainly of formic acid.
The choice of acid depends on the price and pre-treatment conditions. Very
volatile acids, such as formic acid, can cause irritation if used without
proper
protection. The lime content of the pressed pulp is preferably low, i.e. no
lime

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or aluminium is added to the beet pulp (the cossette) to facilitate the
pressing
at the final stage of the sugar (saccharose) separation process. After the
pressing the temperature of the pulp is about 60°C and pre-treatment is
car-
ried out preferably immediately after the pressing before the pulp cools off.
The pre-treated pulp having a pH of about 4 is preferably packaged
in air-tight storage and allowed to stabilize. The tight storage can be e.g. a
plastic bag or tube made of polyethene, or what is known as a flat silo. The
protection prevents light and air (oxygen) from accessing the treated pulp.
The
enzyme activity of lactic acid bacteria present in the fresh pulp causes oxida-
tion of free sugars during the stabilization. Organic acids, mainly lactic
acid,
are formed. The deoxidizing reaction with acid formation as a result removes
oxygen and free sugars from the material and prevents further fermentation of
the pulp. The obtained pulp, preferably having a pH of 3.5 to 4.5 (most pref-
erably 3.9 to 4.3) and 20 to 27 percent by weight of dry substances, is stored
air-tightly at a non-elevated temperature, where it is stable for at least a
year.
The concept "air-tightly" refers to the pulp being stored in e.g. plastic bags
or
tubes having a volume of 50 to 200 m3, or a sealed flat silo.
Said stable pulp is preferably prepared from pulp which has been
pressed without lime or aluminium addition. The composition of stable pulp is
typically: cellulose and lignin about 30 percent by weight, hemicellulose
about
70 percent by weight, of which a third is pectin, pH about 4. This raw
material
is available throughout the year, its preparation is inexpensive and storage
easy. The composition of the raw material is advantageous since it does not
include low molecular weight sugars, saccharose or glucose.
EXAMPLES
Example 1. Preparation of pectin
Fresh pressed pulp with no addition of lime and with a dry sub-
stance content of about 22% was contacted with a commercial acid mixture
"Ensimax" (manufacturer: Kemira Oy, Finland); 4 litres of acid mixture per 1
ton of pressed pulp. Said acid mixture contained 30 percent by weight of for-
mic acid (85%), 20 percent by weight of acetic acid (80%) and 50 percent by
weight of lignosulphonate (37%). During mixing the temperature of the pulp
was 50 to 60°C and it was mixed for about 1 minute in a screw mixer.
The
mixture was packaged in a tight plastic bag made from 0.25 mm polyethene
film. The inner surface of the film was black and the outer surface white, pro-

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viding efficient protection for the pulp against light and oxygen. The pulp
was
allowed to cool off and stabilize outdoors and the bags were stored in an out-
door storage.
The treated pulp, which had been stored for about 6 months, was
used as raw material for sugar beet pectin. The composition of the pulp was
as follows: 25 percent by weight of dry substance, Ensimax 0.4 percent by
weight, free sugars below 1 percent by weight. Acid hydrolysis was performed
first: pH 1.5, temperature 70°C. The hydrolysate was neutralized with
sodium
carbonate to pH 3, and the solution was separated from insoluble pulp by a
decanting centrifuge and filtered by what is known as precoat filtration in
the
presence of a filtration additive. The filtered solution was concentrated by
evaporation below fi0°C to a dry substance content of 9 percent by
weight.
Pectin was precipitated from the concentrated solution by addition of isopro-
panol so that the solution contained 75 percent by weight of isopropanol. The
precipitated pectin was washed with a 60% isopropanol solution, separated by
centrifugation and dried in an air current at 50°C. The yield was 15
percent by
weight of pectin of pulp dry substance.
Example 2. Preparation of araban
Fresh pressed pulp was pre-treated as in Example 1 and the pre-
treated stable pulp was taken out of storage after 8 months. The pulp was hy-
drolyzed at pH 12, temperature 95°C, by addition of milk of lime. The
hydro-
lysate was neutralized with carbon dioxide and the pulp was separated from
the solution by a filter press. After concentration the araban in the filtrate
was
separated from salts and other substances by chromatography using a poly-
styrenedivinylbenzene separation resin. The araban fraction was evaporated
and dried. The yield of crude araban was 20 percent by weight.
Example 3. Preparation of L-arabinose
Fresh pressed pulp was pre-treated as in Example 1 and the stable
pulp was taken from storage after 7 months. The pulp was hydrolyzed with
milk of lime as in Example 2, neutralized, and filtered. The solution was then
concentrated by evaporation and the araban was hydrolyzed into L-arabinose
by addition of sulphuric acid to pH 0.8 and by heating to 90°C. The
hydrolyzed
solution was neutralized with sodium hydroxide to pH 6 and the sulphate pre-
cipitate formed in the neutralization was removed by filtration. The arabinose
fraction was separated by chromatography using a polystyrenedivinylbenzene
separation resin in Na form. The arabinose solution was further purified with

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cation and anion exchange and a colour removal resin (Optipore) and evapo-
rated, whereby the L-arabinose was crystallized. The crystals were separated
from the mother liquor by centrifugation. The yield was about 15 percent by
weight of L-arabinose of pulp dry substance.
5 Example 4. Preparation of araban and arabinose
Fresh pressed pulp was treated and pectin was precipitated with
isopropanol as in Example 1. Free L-arabinose and arabinogalactan-poly-
saccharide remained in the filtrates and washing solutions generated in the
preparation of pectin. Isopropanol was removed from the solution by distilla-
tion; whereupon the polysaccharides were separated by chromatography from
the L-arabinose using a separation resin either directly or after acid
hydrolysis
of the arabinogalactan polymers performed to increase the L-arabinose con-
tent. The L-arabinose was crystallized from the monosaccharide fraction as in
Example 3 and the araban was prepared by purification and drying from the
non-hydrolyzed polymer fraction as in Example 2.